View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Digital.CSIC Thallium in coal: Analysis and Environmental implications M. Antonia López Antón1, D. Alan Spears2 , Mercedes Díaz Somoano1 M. Rosa Martínez Tarazona1 1.-Instituto Nacional del Carbón (CSIC), C/ Francisco Pintado Fe 26, 33011, Oviedo Spain 2.-University of Sheffield, Sheffield S102TN, UK. Corresponding author: [email protected] Key words: Thallium in coal, Analysis of Thallium, Thallium in coal combustion Abstract The ecotoxicological importance of thallium stems from its acute toxicity, the effects of which are as harmful to living organisms as those of lead and mercury. The main anthropogenic sources of thallium are the emissions from coal combustion processes, underlining the need to control this element in coal and coal by-products. Despite the threat posed by thallium, very little information has been published on its behaviour in coal-fired power plants or on its modes of occurrence in coal, its mobilisation and its distribution. Although thallium is highly toxic, the environmental risk presented by this element in coal utilization have been studied to a much lesser degree than in the case of other toxic elements such as lead, cadmium or mercury. The present work addresses the issue of thallium in coal, focussing on its origin, modes of occurrence, the analytical methods commonly used for its determination and its behaviour during coal utilization for energy production. 1 Introduction: The importance of evaluating thallium behaviour in coal The toxic effects of thallium (Tl) have long been recognized and have been frequently observed in animals and humans. Although the precise mode of toxicity is unclear [1], it has been reported to be an element that is more acutely toxic than lead, mercury and cadmium [2-3]. It has been suggested that Tl may interfere with vital potassium-dependent processes, since thallium ions and potassium ions are similar in size [4]. Thallium remains in the air, water, and soil for a long time and does not decompose. Some Tl compounds are washed down by the rain and snow into the soil and plants. Eventually it enters the food chain and accumulates in fish and shellfish [5]. Thallium occurs in two oxidation states, Tl(I) and Tl(III), the latter being more toxic. The oxidation state of Tl affects its complexation and subsequent bioavailability and toxicity [6-7]. Early literature claims that Tl (I) is the most abundant species in nature and suggests that trivalent Tl(III) is unlikely [8]. Although the thermodynamic stability supports this claim, there is evidence that the most abundant Tl species in sea and lake waters is Tl(III) [9-11]. The oxidation of Tl(I) to Tl(III) in the environment has been reported to be due to the activity of bacteria [12]. In accordance with Twining et al [7], planktonic bacteria are responsible for oxidizing the thermodynamically stable Tl(I) to the more abundant Tl(III). Exposure to high levels of Tl can have harmful effects on the health [2, 13]. Some of the effects of Tl poisoning include: hair loss, the gradual development of mild gastrointestinal disturbances, encephalopathy, tachycardia degenerative changes in the heart, liver and kidney, alterations of the central nervous and cardiovascular systems and eventually death [14-18]. Thallium is considered a priority pollutant by the Environmental Protection Agency (EPA) of the United States (US), and has been classified as a dangerous substance by the European Union (Directive 67/548/EEC). 2 The industrial facilities that produce or use Tl and its compounds are not the major sources of Tl release to the environment. The main sources are industrial processes where Tl is present as an impurity in the raw materials. This is the case of coal-fired power plant, smelting operations (mainly lead and zinc) and the cement industry [19- 20]. It is estimated that about 2.000-5.000 tons per year of Tl are mobilised by these industrial processes, and in the US about 1000 tons of Tl are released annually into the environment, 350 tons of which are emitted in the form of vapours and dusts, 60 tons bound to non-ferrous metals and more than 500 tons in fluid and solid wastes. From the available data it can be inferred that power generating plants are the main sources of Tl emission into the atmosphere [21-23]. Thallium concentration in most coals ranges from 0.5 to 3 mg kg-1 and it has been calculated that about half of this is emitted into the atmosphere [24]. Emissions of Tl in the flue gases of coal-fired power-generating plants may amount to 700 µg m-3, reaching up to 2500 µg m-3 in those from cement plants. In the case of cement plants, coal is not the main source of Tl. The raw materials used for cements such as ashes or certain additives may contain higher amounts of Tl than coal. Generally speaking in both coal combustion and cement production, Tl volatilizes at high temperatures and condenses on the surface of ash particles in the cooler parts of the system. As a result, Tl could be 2 to 10 times more concentrated in the fly ashes than it was in the coal before combustion [25-26]. The concentrations of Tl reported to be emitted on airborne fly ash from coal-burning power plants range from 29 to 76 μg g-1, and these increase with decreasing particle size. The highest concentrations have been found on particles with a size of less than 7.3 μm in diameter. Such particles are the most dangerous since they are able to pass through conventional particle retention devices in power-generating plants and remain suspended in the atmosphere. They may eventually be deposited in the lower respiratory tract [25, 27]. 3 There are not regulations for the Tl content of ambient air. However, the EPA has established a maximum contaminant level (MCL) for Tl in drinking water and waste water (effluent) of 0.002 and 0.14 mg L-1, respectively. Moreover there is a threshold limit value (TLV) of 0.1 mg m-3 for Tl in the air of any work place. This standard has been adopted by the Occupational Safety and Health Administration (OSHA) and has been signed by the American Conference of Governmental Industrial Hygienists (ACGIH). In addition to these regulations, the EPA requires that discharges or accidental spills into the environment of 1.000 pounds or more of Tl be reported and the National Institute for Occupational Safety and Health (NIOSH) has recommended that 15 mg m-3 of Tl be considered as an immediate threat to life and health [2, 22, 28-29]. Methods for analysis of thallium in coal and sub-products Several methods are available for determining of Tl, their effectiveness depending on the type and quantity of the sample to be analysed [25, 29]. Techniques such as inductively coupled mass atomic emission spectrometry (ICP-AES), graphite furnace atomic spectrometry (GF-AAS), radiochemical neutron activation analysis (NAA) or inductively coupled plasma mass spectrometry (ICP-MS) have been used to determine Tl in meat and food products, urine and blood, biological and environmental samples and water [19, 30-32]. These techniques have sufficient detection limits (0.1 µg kg-1) and are well-suited to applications where a high degree of sensitivity is required for small amounts of sample. For the analysis of Tl in coal and coal combustion by- products several methods of analysis have been evaluated including some of the techniques mentioned above [33-35]. In all of them it is necessary to perform a very careful sample preparation procedure to avoid the loss of Tl or to get out of any contamination. The collection and treatment of the sample prior to analysis requires 4 special attention in the case of coal as there is a lack of certified reference materials (CRMs) for Tl in coal samples ([36]. Thallium is almost always determined as total metal for which, in most of the techniques already mentioned, the samples need to be in solution. In the case of coal samples the first step is to oxidize of the organic matter usually by combustion at low temperatures (300-500ºC), in order to obtain the ashes. These are then subjected to acid digestion by means of a mixture of concentrated hydrofluoric and nitric acids in order to extract the Tl. Digestion must be carried out in a closed vessel to avoid losses from volatilization. Nowadays digestion in Teflon high pressure digestion vessels in microwave ovens is the simplest and quickest option. Alkaline fusion with lithium metaborate followed by dissolution in acid is also a well- known method to bring coal ashes into solution. However, this method entails the risk of losses of Tl due to volatilisation. When four methods for decomposing coal fly ash samples using only nitric acid or a mixture of nitric, hydrochloric and hydrofluoric acids were compared, the best results were obtained using a mixture of acids for digestion in a microwave oven [34-37]. The complete decomposition of the fly ashes was not achieved when only nitric acid was used and occasional losses of Tl occurred when a bomb instead a microwave oven is employed. In general, the direct analysis of solid samples has a number of advantages over analysis in solution. For example, the risk of contamination or loss of analyte is less likely [38]. However, these methods also have important limitations such as the manner of sample introduction, which can be problematic and a more complex method of calibration. [39]. Unsatisfactory results were found when Tl was analyzed in a coal by direct solid sampling in a conventional GFAAS device using deuterium background correction [35].